Microbicidal composition

ABSTRACT

The invention relates to a microbicidal composition which comprises a mixture of at least two components, the first component being 2-methyl-3-isothiazolone (MIT) and the second component being at least one active compound selected from the following groups of active compounds: a) compound having activated methylol groups b) quats or polyquats c) carbamates d) organic acids e) aromatic alcohols.

The invention relates to a microbicidal composition which comprises amixture of at least two components, the first component being2-methyl-3-isothiazolone (MIT).

MIT is also described by the CAS No. 2682-20-4.

The abovementioned microbicidal compositions have been disclosed, forexample, by European patent 1 332 675 in which a commercially availablemicrobicidal benzoic acid is used as second component.

The combination described in this European patent restricts theapplication of MIT with respect to the pH range.

It is an object of the present invention to provide microbicidalcompositions as described above whose application is possible in as widea pH range as possible.

To achieve this object the invention proceeds from a microbicidalcomposition as described at the outset and proposes that this comprisesa mixture of at least two components, the first component being2-methyl-3-isothiazolone and the second component being at least oneactive compound selected from the following groups of active compounds:

a) compounds having activated methylol groups

b) quats or polyquats

c) carbamates

d) organic acids

e) aromatic alcohols

The abovementioned groups of active compounds are in each case likewisebiocidal or microbicidal. They frequently have an altered antimicrobialspectrum. Precisely in combination with MIT, resultant synergisticeffects are produced thereby, since a greater bandwidth of organisms canbe actively combated. The selection of the proposed active compounds issuch that they can also be used in a wide pH range in accordance withthe desired use. The invention therefore combines a broad antimicrobialactivity spectrum with a wide pH application range.

In particular, it is proposed that the inventive composition is usable,for example, in the pH range from 4 to 10.

Different active compounds also have a different mechanism of action.This therefore results in the fact that, for example, one variety oforganisms can be attacked by various active compound mechanisms and asynergistic effect can also thus be produced.

The inventive microbicidal composition is used in domestic products, forexample cleaners, dishwashing agents, cleaning agents, cosmeticproducts, shampoos, soaps, wet wipe uses, for example using moist clothsand the like. Likewise, the inventive composition can also be used inindustrial applications, for example in coatings, paints, plasters,emulsions, dispersions, glues, latex and the like.

It is proposed according to the invention that the composition is amixture of at least two components. The invention does not exclude themicrobicidal composition also having more than two components, MIT thenbeing combinable with two or more further active compounds from the saidgroup selected compounds. It is also possible that a plurality of activecompounds of one group of active compounds are used in an inventivecomposition. The field of application of such a microbicidal compositioncan thereby be further optimized and adapted for the specificapplication. The previously described mechanisms with respect to pH anddifferent possibilities of attacking the harmful organisms apply here inan unmodified manner.

A preferred variant of the invention provides that the compositioncomprises one or more different solvents.

A variant of the invention provides that water, glycols and/or glycolethers are provided as solvent.

A further development according to the invention proposes that asynergistic action of the components present in the mixture is provided.

A preferred variant of the invention provides that an activityenhancement is provided by the solvent, in particular the glycols and/orglycol ethers.

It has been found that the proposed solvents, without having activity oftheir own, improve the activity of the active compounds used. Thiseffect is described and taken to mean hereinafter activity enhancement.

The inventive compositions are used in specific applications whichcontain, for example, various liquid phases. For example, in anoil-water mixture, an oil phase occurs in addition to a water phase. Theharmful organisms to be attacked are situated in the water phase or theboundary layer. The use of the proposed solvents means that the activecompounds also preferably remain in the aqueous phase and can destroymicroorganisms there.

Improved activities of the active compounds used finally result fromimproved active compound uptakes into the respective organisms with theproposed solvents. The concentration of the active compounds used can berestricted, which decreases costs.

In particular, such activity enhancements have been observed with1,2-octanediol, pentylene glycol and hexylene glycol. Generally thisproperty, however, is assigned to the entire group of glycols or glycolethers as solvents.

An inventive variant provides that bronopol, diazolidinylurea orimidazolidinylurea are provided as compounds having activated methylolgroups.

A further development of the invention proposes that polyaminopropylbiguanide, cetrimonium bromide or benzalconium chloride are provided asquats or polyquats.

A preferred variant of the invention provides that iodopropynylbutylcarbamate or dithiocarbamate are provided as carbamates.

An inventive variant provides that dehydroacetic acid, undecylenic acidor salicylic acid are provided as organic acids.

A further development of the invention proposes that phenoxyethanol,phenylethanol, phenoxypropanol, phenylpropanol or dichlorobenzyl alcoholare provided as aromatic alcohols.

A preferred variant of the invention provides that polypropylene glycol2-methyl ether, 1,2-octanediol, propylene glycol, pentylene glycol,hexylene glycol, dipropylene glycol, dipropylene glycol monomethylether, oligo- or polyethylene glycols or polypropylene glycols areprovided as glycols or glycol ethers. Polypropylene glycol is alsocalled PPG-2-methyl ether.

An inventive variant provides that the weight ratio between2-methyl-3-isothiazolone and the other components is between 1:1000 and200:1, preferably between 2:100 and 5:1.

As described, the use of MIT in proportion to the other component variesover a wide range. Here, in the desired field of use, an appropriatecombination is possible by which, obviously, by corresponding controland skilful selection of the active compounds, the total costs of aninventive composition can be greatly reduced.

A further development of the invention proposes that the weight ratiobetween the components and the solvent is between 1:100 and 100:1,preferably 1:10 to 3:2.

A preferred variant of the invention provides the weight percentage ofglycol or glycol ether of the composition is from 0% to 85%.

An inventive variant provides that the weight percentage of1,2-octanediol of the composition is from 0% to 10%.

A further development of the invention proposes that the weightpercentage of 2-methyl-3-isothiazolone in the composition is from 0.1%to 20%, preferably approximately 2% to 8%.

A preferred variant of the invention provides that the weight percentageof aromatic alcohols of the total composition is from 0% to 99.9%,preferably 0.1% to 80%.

An inventive variant provides that the weight percentage of water of thetotal composition is from 0% to 99.9%.

A further development of the invention proposes that the composition isessentially free from halogenated isothiazolone.

The microbicidal compositions of the present invention are essentiallyfree from halogenated isothiazolones. “Essentially” free is taken tomean that the composition has from 0 to at most 3%, preferably from 0 to1%, and further preferably from 0 to only 0.5%, halogenatedisothiazolones (based on the weight), based on the combined weight ofhalogenated isothiazolone and MIT. A further concentration ofhalogenated isothiazolone is unstable and requires additionalstabilization components. These can be, for example, metal salts and thelike which, however, cause additional costs and also can lead toundesirable side effects in subsequent formulation. It is thereforeexpedient, based on the MIT, to provide a weight percentage as low aspossible, as described, of halogenated isothiazolone.

In particular, the finished use formulation is sought to have at maximuma halogenated isothiazolone content of 1000 ppm.

The table below describes various exemplary samples according to theinvention:

Weight Components of the percentage weight percentages Sample Component[%] [%] 1 MIT  5 0.1 . . . 20 Diazolidinylurea 50 20 . . . 60 Water 45 0. . . 79.9 2 MIT  5 0.1 . . . 20 Bronopol 10 0.1 . . . 20 Phenylethanol30 0 . . . 80 PPG-2-methyl ether 35 0 . . . 99.9 Water 20 0 . . . 99.9 3MIT 2-5  0.1 . . . 20 Phenylethanol 50-80  0 . . . 99.9 1,2-octanediol0-10 0 . . . 50 PPG-2-methyl ether 6-30 0 . . . 99.9 Water 2-15 0 . . .99.9 4 MIT 2-5  0.1 . . . 20 Cetrimonium bromide 5-20 0.1 . . . 20Phenylethanol 0-76 0 . . . 99 1,2-octanediol 0-10 0 . . . 50PPG-2-methyl ether 0-35 0 . . . 99.9 Water 2-85 0 . . . 99.9 5 MIT 2-5 0.1 . . . 20 Polyaminopropyl 10 0.1 . . . 40 biguanide Phenylethanol25-30  0 . . . 99.9 PPG-2-methyl ether 15-16  0 . . . 99.9 Water 42-45 0 . . . 99.9 6 MIT  5 0.1 . . . 20 Dichlorobenzyl alcohol 40 0 . . . 55Phenylethanol — 0 . . . 50 PPG-2-methyl ether 0-50 0 . . . 99.91,2-propylene glycol 0-50 0 . . . 99.9 Water  5 0 . . . 20 7 MIT  5 0.1. . . 20 Iodopropynyl  5 0.1 . . . 20 butylcarbamate Phenylethanol 0-500 . . . 99.9 PPG-2-methyl ether 0-25 0 . . . 99.9 1,2-propylene glycol0-85 0 . . . 99.9 Water 5-15 0 . . . 99.9 8 MIT  5 0.1 . . . 20Dehydroacetic acid  8 0.1 . . . 10 Phenylethanol 82 0 . . . 99.9PPG-2-methyl ether — 0 . . . 99.9 1,2-propylene glycol — 0 . . . 99.9Water  5 0 . . . 99.9

The reported weight percentages relate to the total weight of thecomposition. The table above gives an overview of the inventivecompositions which exhibit the desired properties. The table is to betaken to mean that the compositions having the reported weightpercentages (in the 3rd column) lead to a stable composition.

Instead of phenylethanol, it is also provided according to the inventionto use other aromatic alcohols (see their list). In addition, for thevarious samples in the last column a bandwidth of weight percentages ofthe individual components is reported. Reference is explicitly made tothe fact that all combinations mentioned here are considered conjointlydisclosed. If the bandwidth starts at 0%, there are also formulationproposals in which the respective component is not a member of therespective composition. However, reference is made explicitly to thefact that a small fraction, for example 0.1% of the respectivecomponent, is also explicitly considered disclosed for all respectivecomponents and to this extent an interval restricted in this respect,also, for example, from 0.1 to 99.9%, is a preferably restrictedinterval.

The weight percentages are to be taken to mean preferred embodiment ofthe invention and likewise do not restrict the more broadly wordedbandwidth of the weight percentages belonging to the invention.

Synergy tests were conducted using microbiological standard methods.Ringer's Solution (Merck, VWR) was used for testing bacteria, yeast andmould species. In jars 100 ml aliquots of sterile Ringer Solution aredosed with the preservatives and a known inoculum of the single testspecies is added. A control sample containing no preservative is alsoused to ascertain the biocide effect on the inoculum. The prepared jarswere incubated at 30° C. Aliquots are streaked out at regular intervalson specific nutrient agar so that an estimate of kill time can bedetermined at the same time as effective concentration. TSA (tryptic soyagar) was used for bacteria; MEA (malt extract agar) was used for yeastand moulds. The plates were visually evaluated for microbial growth todetermine the MIC after various incubation times at 30° C.

The synergy of the combinations of the present invention was determinedagainst four bacteria, Pseudomonas aeruginosa, Escherichia coli, ProteusMirabilis, AND Staphylococcus aureus, a yeast, Candida albicans and twomoulds Trichoderma viride and Aspergillus niger. The singlemicro-organisms were used at a concentration of about 10⁵ microbes perml. these micro-organisms are standard reference organisms andrepresentative of natural contaminants in many consumer and industrialapplications.

The test results for demonstration of synergy of the preservativecombinations of the present invention are shown below. In each testfirst component (A) was MIT and the second component wasphenylethylalcohol (B).

Phenyl- ppm Phenyl- ppm ethyl- ethyl- MIT MIT alcohol alcoholMicroorganism QA Qa Qb QB SI* Pseudomonas Test 1 50 25 250 2000 0.63Aeruginosa Test 2.1 25 12.5 125 2500 0.55 Test 2.2 25 12.5 125 2500 0.55Test 2.3 25 12.5 125 2500 0.55 Escherichia Test 1 50 25 250 2000 0.63Coli Test 2.1 25 12.5 125 2500 0.55 Test 2.2 25 12.5 125 2500 0.55 Test2.3 25 12.5 125 2500 0.55 Proteus Test 1 50 25 250 2000 0.63 mirabilisTest 2.1 25 12.5 125 2000 0.56 Test 2.2 25 12.5 125 2000 0.56 Test 2.325 12.5 125 2000 0.56 Staphylococcus Test 1 75 25 250 2000 0.46 aureusTest 2.1 50 25 250 1500 0.67 Test 2.2 50 12.5 125 1500 0.33 Test 2.3 5012.5 125 1500 0.33 Candida Test 1 50 25 250 2000 0.63 albicans Test 2.150 25 250 2500 0.60 Test 2.2 50 25 250 1500 0.67 Test 2.3 50 12.5 1251500 0.33 Aspergillus Test 1 50 25 250 1500 0.67 Niger Test 2.1 50 37.5375 2000 0.94 Test 2.2 50 25 250 2000 0.63 Test 2.3 50 37.5 375 20000.94 Trichoderma Test 1 75 25 250 2000 0.46 viride Test 2.1 50 25 2503000 0.58 Test 2.2 50 25 250 3000 0.58 Test 2.3 50 25 250 3000 0.58 *SI= Synergy Index Formula SI = Qa/QA + Qb/QB QA = concentration ofcompound A (first component in ppm, acting alone, which produced an endpoint (MIC of Compound A) Qa = concentration of compound A in ppm, inthe mixture, which produced an end point QB = concentration of compoundB (second component in ppm, acting alone, which produced an end point(MIC of Compound B) Qb = concentration of compound B in ppm, in themixture, which produced an end point Test one was done as single test,Test 2 was performed under statistical conditions with 3 parallelsamples Result: all SI indices show values below 1 sometimes even below0.5formulation based on 2-Methyl-isothiazolin-3-one and Phenvlethylalcohol

immediatly after preperation sample sample 1 sample 2 sample 3 sample 4appearance colorless, colorless, colorless, colorless, clear liquidclear liquid clear liquid clear liquid smell flowery flowery floweryflowery characteristic characteristic characteristic characteristicHazen 25 20 23 21 Gardner 0 0 0 0 content 2-Methyl-isothiazolin-3-one %5.0 5.1 5.0 5.0 phenylethylalcohol % 49.8 49.8 49.7 49.8 4 weeks roomtemperatures dark 4 weeks room temperatures on the window east sidesample 1 sample 2 sample 3 sample 4 sample 1 sample 2 appearancecolorless, colorless, colorless, colorless, colorless, colorless, clearliquid clear liquid clear liquid clear liquid clear liquid clear liquidsmell flowery flowery flowery flowery flowery flowery characteristiccharacteristic characteristic characteristic characteristiccharacteristic Hazen 51 45 50 46 56 56 Gardner 0.1 0.1 0.1 0.1 0.1 0.1content 2-Methyl-isothiazolin-3-one % 5.0 5.0 4.9 5.0 4.9 4.9phenylethylalcohol % 49.9 50.2 50.3 50.1 49.5 49.3 4 weeks roomtemperatures on the window east side 4 weeks 40° C. dark sample 3 sample4 sample 1 sample 2 sample 3 sample 4 appearance colorless, colorless,colorless, colorless, colorless, colorless, clear liquid clear liquidclear liquid clear liquid clear liquid clear liquid smell floweryflowery flowery flowery flowery flowery characteristic characteristiccharacteristic characteristic characteristic characteristic Hazen 76 55188 186 178 180 Gardner 0.2 0.1 0.8 0.8 0.8 0.8 content2-Methyl-isothiazolin-3-one % 4.8 4.9 5.0 4.9 4.8 4.9 phenylethylalcohol% 50.2 49.8 50.8 49.0 50.6 50.0 6 months room 12 months roomtemperatures 6 months 6 months temperatures 12 months 12 months glasscabinet 30° C. dark 8° C. dark glass cabinet 30° C. dark 8° C. darksample 4 sample 4 sample 4 sample 4 sample 4 sample 4 appearancecolorless, yellowish, colorless, colorless, yellowish, colorless, clearliquid clear liquid clear liquid clear liquid clear liquid clear liquidsmell flowery flowery flowery flowery flowery flowery characteristiccharacteristic characteristic characteristic characteristiccharacteristic Hazen 150 245 89 333 470 134 Gardner 1.0 1.8 0.3 1.9 30.8 content 2-Methyl-isothiazolin-3-one % 5.03 4.88 5.05 4.97 5.01 5.01phenylethylalcohol % 50.11 50.16 50.77 50.28 50.18 50.21formulation based on 2-Methyl-isothiazolin-3-one, Dehydroacetic Acid andPhenylethylalcohol

immediatly after preperation sample sample 1 sample 2 sample 3 sample 4appearance colorless, colorless, colorless, colorless, clear liquidclear liquid clear liquid clear liquid smell flowery flowery floweryflowery characteristic characteristic characteristic characteristicHazen 228 248 246 241 Gardner 1.1 1.3 1.2 1.3 content2-Methyl-isothiazolin-3-one % 5.0 5.1 5.0 5.0 Dehydroacetic Acid % 7.98.0 8.0 8.0 phenylethylalcohol % 81.6 81.6 81.7 81.7 4 weeks roomtemperatures dark 4 weeks room temperatures on the window east sidesample 1 sample 2 sample 3 sample 4 sample 1 sample 2 appearancecolorless, colorless, colorless, colorless, colorless, colorless, clearliquid clear liquid clear liquid clear liquid clear liquid clear liquidsmell flowery flowery flowery flowery flowery flowery characteristiccharacteristic characteristic characteristic characteristiccharacteristic Hazen 361 341 354 352 >1000 >1000 Gardner 2 1.9 1.9 1.95.1 4.9 content 2-Methyl-isothiazolin-3-one % 4.8 4.9 4.7 4.8 4.8 4.9Dehydroacetic Acid % 7.7 7.6 7.8 7.7 7.6 7.7 phenylethylalcohol % 81.782.5 82 81.8 82.0 82.4 4 weeks room temperatures on the window east side4 weeks 40° C. dark sample 3 sample 4 sample 1 sample 2 sample 3 sample4 appearance colorless, colorless, colorless, colorless, colorless,colorless, clear liquid clear liquid clear liquid clear liquid clearliquid clear liquid smell flowery flowery flowery flowery floweryflowery characteristic characteristic characteristic characteristiccharacteristic characteristic Hazen 965 >1000 843 860 849 855 Gardner4.6 4.8 4.3 4.3 4.3 4.4 content 2-Methyl-isothiazolin-3-one % 4.8 4.94.4 4.4 4.1 4.3 Dehydroacetic Acid % 7.7 7.7 7.7 7.7 7.8 7.7phenylethylalcohol % 82.1 82.2 82.3 82.5 80.7 81.9 6 months room 12months room temperatures 6 months 6 months temperatures 12 months 12months glass cabinet 30° C. dark 8° C. dark glass cabinet 30° C. dark 8°C. dark sample 4 sample 4 sample 4 sample 4 sample 4 sample 4 appearancecolorless, yellowish, colorless, colorless, yellowish, colorless, clearliquid clear liquid clear liquid clear liquid clear liquid clear liquidsmell flowery flowery flowery flowery flowery flowery characteristiccharacteristic characteristic characteristic characteristiccharacteristic Hazen >1000 >1000 880 >1000 >1000 >1000 Gardner 5.5 5.34.3 7.6 8.6 6.1 content 2-Methyl-isothiazolin-3-one % 3.81 3.02 4.33 3.52.5 4.3 Dehydroacetic Acid % 6.8 5.92 7.38 6.7 5.6 7.3phenylethylalcohol % 78.16 77.24 81.91 82.7 81.9 82.8

1. Microbicidal composition which comprises a mixture of at least twocomponents, the first component being 2-methyl-3-isothiazolone and thesecond component being at least one active compound selected from thefollowing groups of active compounds: a) compounds having activatedmethylol groups b) quats or polyquats c) carbamates d) organic acids e)aromatic alcohols.
 2. Composition according to claim 1, characterized inthat the composition comprises one or more different solvents. 3.Composition according to claim 2, characterized in that water, glycolsand/or glycol ethers are provided as solvent.
 4. Composition accordingto claim 1, characterized by a synergistic action of the componentspresent in the mixture.
 5. Composition according to claim 3,characterized by an activity enhancement by the solvent.
 6. Compositionaccording to claim 1, characterized in that bronopol, diazolidinylureaor imidazolidinylurea are provided as compounds having activatedmethylol groups.
 7. Composition according to claim 1, characterized inthat polyaminopropyl biguanide, cetrimonium bromide or benzalconiumchloride are provided as quats or polyquats.
 8. Composition according toclaim 1, characterized in that iodopropynyl butylcarbamate ordithiocarbamate are provided as carbamates.
 9. Composition according toclaim 1, characterized in that dehydroacetic acid, undecylenic acid orsalicylic acid are provided as organic acids.
 10. Composition accordingto claim 1, characterized in that phenoxyethanol, phenylethanol,phenoxypropanol, phenylpropanol or dichlorobenzyl alcohol are providedas aromatic alcohols.
 11. Composition according to claim 3,characterized in that polypropylene glycol 2-methyl ether,1,2-octanediol, propylene glycol, pentylene glycol, hexylene glycol,dipropylene glycol, dipropylene glycol monomethyl ether, oligo- orpolyethylene glycols or polypropylene glycols are provided as glycols orglycol ethers.
 12. Composition according to claim 1, characterized inthat the weight ratio between 2-methyl-3-isothiazolone and the othercomponents is between 1:1000 and 200:1.
 13. Composition according toclaim 2, characterized in that the weight ratio between the componentsand the solvent is between 1:100 and 100:1.
 14. Composition according toclaim 3, characterized in that the weight percentage of glycol or glycolether in the composition is from 0% to 85%.
 15. Composition according toclaim 11, characterized in that the weight percentage of 1,2-octanediolin the composition is from 0% to 10%.
 16. Composition according to claim1, characterized in that the weight percentage of2-methyl-3-isothiazolone in the composition is from 0.1% to 20%. 17.Composition according to claim 10, characterized in that the weightpercentage of aromatic alcohols in the total composition is from 0% to99.9%.
 18. Composition according to claim 3, characterized in that theweight percentage of water in the total composition is from 0% to 99.9%.19. Composition according to claim 1, characterized in that thecomposition is essentially free from halogenated isothiazolone. 20.Composition according to claim 1, characterized in that the weight ratiobetween 2-methyl-3-isothiazolone and the other components is between2:100 and 5:1.
 21. Composition according to claim 2, characterized inthat the weight ratio between the components and the solvent is between1:10 to 3:2.
 22. Composition according to claim 1, characterized in thatthe weight percentage of 2-methyl-3-isothiazolone in the composition isfrom 2% to 8%.
 23. Composition according to claim 10, characterized inthat the weight percentage of aromatic alcohols in the total compositionis from 0.1% to 80%.